CN107920528A - Composition, the manufacture method of composition and composition pesticide - Google Patents
Composition, the manufacture method of composition and composition pesticide Download PDFInfo
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- CN107920528A CN107920528A CN201680049766.6A CN201680049766A CN107920528A CN 107920528 A CN107920528 A CN 107920528A CN 201680049766 A CN201680049766 A CN 201680049766A CN 107920528 A CN107920528 A CN 107920528A
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- composition
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- pesticide activity
- slightly water
- saponified
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
Abstract
A kind of composition, it includes slightly water-soluble pesticide activity and solid dielectric, the solid dielectric is included containing the saponified of the polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group, and slightly water-soluble pesticide activity is scattered in solid dielectric.
Description
Technical field
The present invention relates to composition, the manufacture method of composition and composition pesticide.
Background technology
There are following medicines among the medicine as pesticide activity：Although it is with excellent pharmacological action,
But it is difficult to be absorbed from root, leaf etc. due to slightly water-soluble, is not fully utilized as pesticide.
On the other hand, as the water miscible technology for improving poorly water soluble drugs, it is known to solid dispersions technique.Generally
For, the solid dispersions of medicine refer to that medicine is scattered in the material formed in solid dielectric (base).
As the base for being used to prepare solid dispersions, it is known that pass through the polymerizable vinyl list such as polyvinyl alcohol and acrylic acid
Polyvinyl alcohol based copolymer obtained from the polymerization of body (for example, see patent document 1).
Prior art literature
Patent document
Patent document 1：International Publication No. 2008/133102
The content of the invention
Problems to be solved by the invention
However, preparing solid dispersions as base even with above-mentioned polyvinyl alcohol based copolymer, it can not say and carry
The water miscible performance of high poorly water soluble drugs is sufficient.
It is an object of the present invention to provide the group for the water miscible excellent performance for improving slightly water-soluble pesticide activity
The manufacture method of compound and such composition.In addition, it is an object of the present invention to provide improve slightly water-soluble pesticide activity
The composition pesticide of the water miscible excellent performance of compound.
The means used to solve the problem
The inventors of the present invention have made intensive studies, it turns out that：By using containing in sulfonic group and sulphonate-base
At least one group polyvinyl acetate it is saponified, the water solubility of slightly water-soluble pesticide activity greatly improves,
So as to complete the present invention.
That is, the present invention provides a kind of composition, described solid it includes slightly water-soluble pesticide activity and solid dielectric
Body medium includes saponified, the shipwreck containing the polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group
Soluble pesticide reactive compound is scattered in solid dielectric.
The water miscible excellent performance of the raising slightly water-soluble pesticide activity of the composition of the present invention.In addition, this
The manufacturing of the composition of invention is also excellent.
In above-mentioned composition, slightly water-soluble pesticide activity and above-mentioned saponified mass ratio (slightly water-soluble pesticide
Reactive compound:It is saponified) can be 7:3~1:15.Thus, the water miscible property of slightly water-soluble pesticide activity is improved
It can further improve.
Above-mentioned saponified saponification degree can be 10~100mol%.Thus, slightly water-soluble pesticide activity is improved
Water miscible performance further improve.
Above-mentioned slightly water-soluble pesticide activity can be flumioxazin (flumioxazin), N- (1,1,3- front threes
Base indane -4- bases) -1- methyl -3- difluoromethyl pyrazole -4- carboxylic acid amides, 1- [2- ({ [1- (4- chlorphenyls) -1H- pyrazoles -3-
Base] epoxide methyl) -3- aminomethyl phenyls] -4- methyl -5- oxos -4,5- dihydros -1H-TETRAZOLE, Guardian (ethaboxam)
Or 2- [3- (ethylsulfonyl) pyridine -2- bases] -5- (trifyl) benzoxazoles.The raising of composition of the present invention water
The water miscible performance of slightly solubility pesticide activity is also excellent.
The manufacture method of the composition of the present invention possesses following processes：Slightly water-soluble pesticide activity and solid are situated between
Matter is dissolved in organic solvent and prepares the process of solution and the process for being spray-dried solution, the solid dielectric bag
Containing containing the saponified of the polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group.The combination of the present invention
The manufacture method of thing possesses following processes：Slightly water-soluble pesticide activity and solid dielectric are obtained by mixing mixture
Process and the process that mixture is carried out to melting extrusion granulation, the solid dielectric, which includes to contain, is selected from sulfonic group and sulfonic acid
The polyvinyl acetate of at least one of alkali group it is saponified.According to these manufacture methods, can easily manufacture
State composition.The composition of the present invention can be manufactured by these manufacture methods.That is, the present invention, which provides, can pass through above-mentioned manufacture
The composition that method obtains.
The composition pesticide of the present invention contains above-mentioned composition.The raising slightly water-soluble pesticide activity of the composition pesticide
The water miscible excellent performance of compound.
The composition pesticide of the present invention can contain above-mentioned composition and aromatic sulphonic acid type high molecular surfactant.Root
According to the composition pesticide, the water solubility of high slightly water-soluble pesticide activity can be more muchly kept.
Aromatic sulphonic acid type high molecular surfactant can be selected from lignosulfonates, alkyl aryl sulphonic acid and formaldehyde
The salt of condensation product, aryl sulfonic acid and formaldehyde condensation product salt and aryl sulfonic acid and alkyl aryl sulphonic acid and formaldehyde contracting
At least one of salt of compound., can be more muchly when aromatic sulphonic acid type high molecular surfactant is such material
Keep the water solubility of high slightly water-soluble pesticide activity.
Slightly water-soluble pesticide activity in above-mentioned composition pesticide can be flumioxazin or 1- [2-
({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls] epoxide } methyl) -3- aminomethyl phenyls] -4- methyl -5- oxo -4,5- dihydros -
1H-TETRAZOLE.
Mass ratio (the slightly water-soluble of slightly water-soluble pesticide activity and aromatic sulphonic acid type high molecular surfactant
Pesticide activity:Aromatic sulphonic acid type high molecular surfactant) can be 2:1~1:10.According to the composition pesticide,
The water solubility of high slightly water-soluble pesticide activity can more muchly be kept.
The effect of invention
According to the present invention it is possible to provide the combination for the water miscible excellent performance for improving slightly water-soluble pesticide activity
Thing.The manufacturing of the composition of the present invention is also excellent.In addition, according to the present invention it is possible to provide the manufacture method of said composition.This
Outside, according to the present invention it is possible to provide the pesticide combination for the water miscible excellent performance for improving slightly water-soluble pesticide activity
Thing and the water miscible composition pesticide that can more muchly keep high slightly water-soluble pesticide activity.
Brief description of the drawings
Fig. 1 is the figure for the powder x-ray diffraction measurement result for representing the powder A that Production Example 1 is related to.
Fig. 2 is the figure for the powder x-ray diffraction measurement result for representing the powder B that Production Example 2 is related to.
Fig. 3 is the figure for the powder x-ray diffraction measurement result for representing the powder C that Production Example 3 is related to.
Fig. 4 is the figure for the powder x-ray diffraction measurement result for representing the powder D that Production Example 4 is related to.
Fig. 5 is the figure for the powder x-ray diffraction measurement result for representing the powder E that Production Example 5 is related to.
Fig. 6 is the figure for the powder x-ray diffraction measurement result for representing the powder F that Production Example 6 is related to.
Fig. 7 is the figure for the powder x-ray diffraction measurement result for representing the powder G that Production Example 7 is related to.
Fig. 8 is the figure for the powder x-ray diffraction measurement result for representing the powder H that Production Example 8 is related to.
Fig. 9 is the figure for the powder x-ray diffraction measurement result for representing the powder I that Production Example 9 is related to.
Figure 10 is the figure for the powder x-ray diffraction measurement result for representing the powder J that Production Example 10 is related to.
Figure 11 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder K that Production Example 11 is related to.
Figure 12 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder L that Production Example 13 is related to.
Figure 13 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder M that Production Example 14 is related to.
Figure 14 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder N that Production Example 15 is related to.
Figure 15 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder O that Production Example 16 is related to.
Figure 16 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder P that Production Example 17 is related to.
Figure 17 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder Q that Production Example 18 is related to.
Figure 18 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder R that Production Example 19 is related to.
Figure 19 is the figure for the powder x-ray diffraction measurement result for representing the comparison powder S that Production Example 20 is related to.
Embodiment
Hereinafter, the suitable embodiment of the present invention is illustrated.But the invention is not restricted to mode is implemented as follows.
The composition that one embodiment is related to includes slightly water-soluble pesticide activity and solid dielectric, the solid
Medium is included containing the saponified of the polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group.Shipwreck is molten
Property pesticide activity is scattered in solid dielectric.The concrete example of above-mentioned composition includes solid dispersions.Said composition
The water miscible performance and manufacturing for improving slightly water-soluble pesticide activity are excellent.Herein, in this specification, shipwreck is improved
The water miscible performance of soluble pesticide reactive compound refers to：During slightly water-soluble pesticide activity being dissolved alone in water
Solubility on the basis of slightly water-soluble pesticide activity solubility in water increase rate.Above-mentioned composition for example may be used
Think particle shape.When above-mentioned composition is particle shape, slightly water-soluble pesticide activity is for example scattered in particle.
Slightly water-soluble pesticide activity can be for example scattered in solid dielectric with crystalline state, can also be with amorphous
Or semi-amorphous state is scattered in solid dielectric.It is water miscible from the water solubility of slightly water-soluble pesticide activity and raising
From the viewpoint of performance further improves, slightly water-soluble pesticide activity can be scattered in amorphous or semi-amorphous state
In solid dielectric.
Whether it is scattered in for slightly water-soluble pesticide activity in solid dielectric with amorphous or semi-amorphous state, according to
Judged according to following (i)~(iv).
(i) to the powder of composition (slightly water-soluble pesticide activity is scattered in the composition formed in solid dielectric)
X-ray diffraction is measured.
(ii) slightly water-soluble pesticide activity and solid dielectric are being protected with the mass ratio same with above-mentioned composition
Hold and mixed under solid state.The powder x-ray diffraction of obtained mixture (physical mixed sample) is measured.Should
In physical mixed sample, observe from the diffraction maximum of the crystallization of slightly water-soluble pesticide activity and/or from solid
The diffraction maximum of the crystallization of body medium.
(iii) by the measurement result of above-mentioned composition compared with the measurement result of physical mixed sample.
(iv) observed in the measurement result of above-mentioned composition in the measurement result unconfirmed in physical mixed sample
From crystallization diffraction maximum in the case of or the diffraction maximum face with being observed in the measurement result of physical mixed sample
In the case that product is reduced compared to diffraction peak areas, it is judged as slightly water-soluble pesticide activity with amorphous or semi-amorphous state
It is scattered in solid dielectric.
Powder x-ray diffraction can for example use X ' Pert PRO MPD (Spectris (Spectris) company system) following
Under the conditions of be measured.
Target：Cu
X-ray tube current：40mA
X-ray tube voltage：45kV
Scanning range：2 θ=4.0~40.0 °
(slightly water-soluble pesticide activity)
In this specification, slightly water-soluble pesticide activity refers to：Water during 25 DEG C among pesticide activity
Solubility is less than the pesticide activity of 200ppm.Pesticide activity is for example, insecticide, fungicide and remove
Careless agent.
As slightly water-soluble pesticide activity insecticide for example,：XMC, sevin (carbaryl),
The carbamate compounds such as fenoxycarb (fenoxycarb), alanycarb (alanycarb)；Phenthoate dimephenthoate cidial (phenthoate), kill
Worm fear (tetrachlorvinphose), dimethylvinphos (dimethylvinphos), zolone (phosalone), chlopyrifos
(chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), pyridaphethione (pyridaphenthion), quinoline sulphur
Phosphorus (quinalphos), triazotion (azinphos-ethyl), methyl azinphos-methyl (azinphos-methyl), salithion
(salithion) organic phosphorus compound such as；Buprofezin, thiocyclam, bensultap, fenoxycarb, fenazaquin, fenpyroximate, pyridaben, volt
Ant hydrazone, Methomyl, capillary, fenpyroximate, pyrimidifen, tebufenozide, tebufenpyrad, indoxacarb MP, sulfluramid, milbemectin and deinsectization
Rhzomorph；Etoxazole Deng oxazoline compounds；And 2- [3- (ethylsulfonyl) pyridine -2- bases] -5- (trifyl) benzo
The benzoazole compounds such as oxazole.
As slightly water-soluble pesticide activity fungicide for example,：Benomyl, carbendazim, thiophene benzene miaow
The benzimidazole compounds such as azoles, thiophanate methyl；The carbanilate compound such as diethofencarb；Procymidone, iprodione, ethene
The dicarboximide compound such as sclex；Olefin conversion, epoxiconazole, Tebuconazole, difenoconazole, cyproconazole, Flusilazole, fluosilicic
The azole compounds such as azoles；Acylalaninies compound；Mepronil, flutolanil, thifluzamide, Guardian, N- (1,1,3- trimethyls
Indane -4- bases) -1- methyl -3- difluoromethyl pyrazole -4- carboxylic acid amides (such as N- (1,1,3- trimethyl indane -4- bases) -1- first
The R bodies enantiomter of base -3- difluoromethyl pyrazole -4- carboxylic acid amides and its 98 of S body enantiomters:2 mixture) etc. first
Amide compound；The organic phosphorus compounds such as tolelofos-methyl, Ppyrazophos；The anilino-pyrimidines such as pyrimethanil, mepanipyrim, cyprodinil
Compound；Cough up the phenylpyrrole compounds such as bacterium ester；Bravo, my acid benzene-S-methyl, Isoprothiolane, diclomezin
(dichlomedin), Pencycuron, azoles furan grass, Delan, chinomethionat, fluorine mepanipyrim, triazine (triazine), biguanides octyl
Benzene sulfonic acid (イ ミ ノ Network タ ジ Application ア Le ベ シ Le acid), cyazofamid, fenhexamid, cyflufenamid, tiadinil, Mancozeb
(manzeb), captan, folpet, probenazole, rabcide, dimethomorph (Dimethomorph), famoxadone, Ao Suoli
Acid, fluazinam, ferimzone and double chlorine zarilamid；And 1- [2- ({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls] epoxide } first
Base) -3- aminomethyl phenyls] methoxyacrylate compound such as -4- methyl -5- oxos -4,5- dihydros -1H-TETRAZOLE.
As slightly water-soluble pesticide activity herbicide for example,：Sigma's piperazine, atrazine, prometryn,
The triaizine compounds such as dimethametryn, triaziflam；The carbamide compounds such as isoproturon；The nitrile compounds such as ioxynil；Trefanocide, amino
The dinitroaniline compounds such as the third fluorine spirit, pendimethalin, oryzalin；The fragrance such as imazaquin, dithiopyr, fentrazamide
Race's carboxylic acid compound；Bensulfuron-methyl, ethoxysulfuron, pyrazosulfuron ethyl ester, azimsulfuron, halosulfuronmethyl, flazasulfuron,
The solsonylurea compounds such as cinosulfuron, nicosulfuron, rimsulfuron 25, imazosulfuron, metsulfuron-methyl, cypromisulfuron, triflusulfuronmethyl；
The N- phenylphthalimide compounds such as flumioxazin, cinidon-ethyl and fluorine imines grass ester；The phonetic sulphur of sulfentrazone, azoles
Careless amine, fenoxaprops, cyhalofop-butyl, Diflufenican, monometflurazone, isoxaflutoles and mefenacet.Herein, above-mentioned carboxylic acid
The concrete example of compound includes the compound for example with carboxyl and the compound with carbonyl.
Above-mentioned slightly water-soluble pesticide activity can be used singly or in combination of two or more.Shipwreck
Soluble pesticide reactive compound for example can be flumioxazin, N- (1,1,3- trimethyl indane -4- bases) -1- methyl -3- two
Methyl fluoride pyrazole-4-carboxamide, 1- [2- ({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls] epoxide } methyl) -3- aminomethyl phenyls] -
4- methyl -5- oxos -4,5- dihydros -1H-TETRAZOLE, Guardian or 2- [3- (ethylsulfonyl) pyridine -2- bases] -5- (fluoroforms
Sulfonyl) benzoxazoles.
The R body enantiomerisms of N- (1,1,3- trimethyl indane -4- bases) -1- methyl -3- difluoromethyl pyrazole -4- carboxylic acid amides
The 98 of body and its S body enantiomters:Water solubility at 25 DEG C of 2 mixture is about 20ppm, at 25 DEG C of Guardian
Water solubility be about 5ppm, water solubility at 25 DEG C of flumioxazin is about 2ppm, 2- [3- (ethylsulfonyl) pyridine-
2- yls] (water solubility at 25 DEG C of trifyl) benzoxazoles is about 6ppm to -5-, 1- [2- ({ [1- (4- chlorobenzenes
Base) -1H- pyrazole-3-yls] epoxide } methyl) -3- aminomethyl phenyls] 25 DEG C of -4- methyl -5- oxos -4,5- dihydros -1H-TETRAZOLE
When water solubility be about 0.03ppm.
(solid dielectric)
As described above, solid dielectric is included containing the poly- second selected from least one of sulfonic group and sulphonate-base group
Saponified (hereinafter sometimes referred to as " sulfonic acid modified polyvinyl acetate saponified ") of vinyl acetate.Sulfonic group and sulphonate-base
Concrete example include formula (I) shown in group.That is, the saponified of sulfonic acid modified polyvinyl acetate for example can be containing formula
(I) polyvinyl acetate of group shown in it is saponified.
-SO3X···(I)
In formula (I), X represents hydrogen atom or monovalent cation.As monovalent cation, for example, alkali metal ion
And ammonium ion.As alkali metal ion, for example, sodium ion and potassium ion.
Sulfonic group of the present embodiment and/or sulphonate-base can be included with the state of free acid.
From the viewpoint of the water miscible performance for improving slightly water-soluble pesticide activity further improves, sulfonic acid changes
Property polyvinyl acetate it is saponified for example can be contain sulfonic group (- SO3H)、-SO3Na、-SO3K or-SO3NH4Poly- acetic acid
Vinyl acetate it is saponified.
The saponified of sulfonic acid modified polyvinyl acetate is, for example, to include to derive to contain to be selected from sulfonic group and sulphonate-base
At least one of the polymerized monomer of group construction unit and formula (II) shown in construction unit (vinyl alcohol structure) height
Molecular compound.
-CH2-CH(OH)-···(II)
The saponified concrete example of sulfonic acid modified polyvinyl acetate, which includes for example being embedded with polyvinyl alcohol skeleton, to be come
Come from the compound that the structure containing the polymerized monomer selected from least one of sulfonic group and sulphonate-base group forms.Separately
Outside, the saponified construction unit (vinyl acetate ester structure) that can contain shown in formula (III) of sulfonic acid modified polyvinyl acetate.
-CH2-CH(OCOCH3)-···(III)
From the viewpoint of the water miscible performance for improving slightly water-soluble pesticide activity further improves, sulfonic acid changes
The saponified saponification degree of property polyvinyl acetate for example can be more than 10mol%, more than 20mol% or more than 30mol%.
From the same viewpoint, the saponified saponification degree of sulfonic acid modified polyvinyl acetate for example can be below 100mol%,
Below 80mol% or below 70mol%.From these viewpoints, the saponified saponification degree of sulfonic acid modified polyvinyl acetate
Such as can be 10~100mol%, or 20~80mol%, or 30~100mol%, or 30~
70mol%.
Slightly water-soluble pesticide activity is N- (1,1,3- trimethyl indane -4- bases) -1- methyl -3- difluoromethyl pyrroles
During azoles -4- carboxylic acid amides, from the viewpoint of permanent holding is water-soluble, above-mentioned saponified saponification degree for example can be 20mol%
More than, or below 100mol%.From these viewpoints, above-mentioned saponified saponification degree for example can be 20~
100mol%.
Herein, saponification degree is construction unit shown in formula (II) relative to shown in construction unit shown in formula (II) and formula (III)
The content in mol of the total amount of construction unit.In this specification, saponification degree represents to calculate according to JIS K 6726-1994
Numerical value.
The saponified degree of polymerization of sulfonic acid modified polyvinyl acetate for example can be more than 50, or 1000 with
Under, less than 700 or less than 500.From these viewpoints, the saponified degree of polymerization of sulfonic acid modified polyvinyl acetate for example may be used
Think 50~1000, or 50~700, or 50~500.
Herein, in this specification, the saponified degree of polymerization of sulfonic acid modified polyvinyl acetate is represented according to JIS K
The numerical value that 6726-1994 is calculated.
The saponified of sulfonic acid modified polyvinyl acetate for example can be by by alkene sulfonic acid or its salt and vinyl acetate
Copolymer obtained from the vinyl esters such as ester are copolymerized further carries out the method for saponification to manufacture.
As alkene sulfonic acid, for example, vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid, maleic acid sulphur
Arrcostab, sulfoalkyl (methyl) acrylamide and (methyl) suphoalkyl acrylate.
Solvent can also be used in copolyreaction.As the solvent, for example, the mixing of alcohol and alcohol and water is molten
Agent.
The concrete example of alkene sulfonic acid or its salt includes the compound shown in formula (1)~(5).
In formula (1), R10Represent alkyl, R11Represent alkylidene, M represents hydrogen atom, alkali metal ion or ammonium ion.
R in formula (2)11It is identical with implication above with M.
In formula (3), R1Represent hydrogen or methyl, R2Represent hydrogen or alkyl.R11It is identical with implication above with M.
In formula (4), R1、R11It is identical with implication above with M.
In formula (5), n represents 1~8 integer.R1It is identical with implication above with M.
The concrete example of compound shown in formula (1) or (2) includes sulfopropyl -2- ethylhexyl maleat sodium (sodium
Sulfopropyl 2-ethylhexyl malate), sulfopropyl tridecyl maleate sodium and sulfopropyl eicosyl Malaysia
Acid esters sodium.
The concrete example of compound shown in formula (3) or formula (4) includes N- sulphur isobutylidene acrylamide sodium salts.
The concrete example of compound shown in formula (5) includes acrylic acid 2- sulphur ethyl ester sodium.
Sulfonic acid modified polyvinyl acetate it is saponified in, on the basis of forming the mole of saponified whole monomers,
Total mole of monomer with sulfonic group and sulphonate-base can be for example more than 0.1mol% or more than 1mol%, also may be used
Think below 30mol%, below 20mol% or below 10mol%.It is above-mentioned saponified complete to form from these viewpoints
On the basis of the mole of portion's monomer, the total mole with the monomer of sulfonic group and sulphonate-base for example can be 0.1~
30mol%, or 0.1~20mol%, or 1~10mol%.
As the saponified of sulfonic acid modified polyvinyl acetate, commercially available product can be used.Gather as commercially available sulfonic acid modified
Vinyl acetate it is saponified, for example,：GOHSENX L-823 (saponification degrees：43.5~49.5mol%, Japan's synthesis
Chemical industry Co. Ltd. system), GOHSENX CKS-50 (saponification degrees：More than 99mol%, Japanese synthetic chemical industry strain formula meeting
Society's system), GOHSENX L-3266 (saponification degrees：86.5~89.0mol%, the Nippon Synthetic Chemical Industry Co., Ltd's system) and ASP-
05A (saponification degrees：88.1mol%, JAPAN VAM＆POVAL Co. Ltd. systems).
Solid dielectric can be included except sulfonic acid modified polyvinyl acetate within the scope of the effect of the invention
Compound beyond saponified.As such compound, for example, polyethylene glycol (PEG), polyvinylpyrrolidone
(PVP), hydroxypropyl cellulose (HPC), hypromellose (HPMC), hydroxypropyl cellulose acetate succinate
(HPMCAS), the copolymer (4 of polyvinyl alcohol (PVA), vinyl acetate and l-vinyl-2-pyrrolidone:6), polyvinyl
Caprolactam and polyvinyl acetate and the copolymer of polyethylene glycol.
The saponified content of sulfonic acid modified polyvinyl acetate in solid dielectric relative to solid dielectric gross mass
Such as can be more than 40 mass %, more than 60 mass % or more than 80 mass %, or below 100 mass %.From this
A little viewpoints are set out, and above-mentioned saponified content can be for example 40~100 mass % relative to the gross mass of solid dielectric, also may be used
Think 60~100 mass %, or 80~100 mass %.
The saponified content of sulfonic acid modified polyvinyl acetate in above-mentioned composition is relative to the total of above-mentioned composition
Quality for example can be more than 30 mass %, more than 50 mass % or more than 70 mass %, or below 90 mass %.From
These viewpoints are set out, and saponified content can be for example 30~90 mass % relative to the gross mass of above-mentioned composition, also may be used
Think 50~90 mass %, or 70~90 mass %.
In above-mentioned composition, from the sight that further improves of water miscible performance for improving slightly water-soluble pesticide activity
Point sets out, (quality of slightly water-soluble pesticide activity)/(the saponified quality of sulfonic acid modified polyvinyl acetate) example
Such as can be more than 1/15 or more than 1/9, or less than 7/3, less than 1/1 or less than 2/3.From these viewpoints, on
State (quality of slightly water-soluble pesticide activity)/(saponified matter of sulfonic acid modified polyvinyl acetate in composition
Amount) for example can be 1/15~7/3, or 1/9~1/1, or 1/9~2/3.That is, from raising slightly water-soluble agriculture
From the viewpoint of the water miscible performance of medicine reactive compound further improves, the slightly water-soluble pesticide activity in above-mentioned composition
The saponified mass ratio of compound and sulfonic acid modified polyvinyl acetate such as can be 7:3~1:15, or 1:1~
1:9, or 2:3~1:9.
(manufacture method of above-mentioned composition)
From the viewpoint of ease of manufacturing, and composition of the present embodiment (a kind of composition, it is molten it includes shipwreck
Property pesticide activity and solid dielectric, the solid dielectric included containing at least one in sulfonic group and sulphonate-base
The polyvinyl acetate of kind of group it is saponified, slightly water-soluble pesticide activity is scattered in solid dielectric) for example can be with
Manufactured by spray drying process, extrusion by melting and ultrasonic wave pressed disc method.
Spray drying process is the method for for example possessing following processes：(A-1) by slightly water-soluble pesticide activity and bag
The process that the saponified solid dielectric of the polyvinyl acetate containing sulfonic acid modified is dissolved in organic solvent and prepares solution；And
(A-2) process for being spray-dried above-mentioned solution.
(A-1) process can for example carry out under room temperature or heating.
(A-1) organic solvent used in process is as long as there is by pesticide activity and sulfonic acid modified polyvinyl acetate
The saponified ability fully dissolved of ester is just not particularly limited, such as the organic solvent that preferred boiling point is less than 100 DEG C.From peace
From the viewpoint of full property, organic solvent can be ketone or alcohols, or acetone, ethanol or their mixed solvent.
(A-2) carried out at a temperature of process is for example more than the boiling point of above-mentioned organic solvent.
(A-2) process can for example use spray dryer.As the spray dryer, for example, buchi is public
Take charge of the mini spray dryer B-290 of the system and spray dryer CL-8i of Ohkawara Kakohki Co., Ltd..
Extrusion by melting is the method for for example possessing following processes：(B-1) by slightly water-soluble pesticide activity and bag
The saponified solid dielectric of the polyvinyl acetate containing sulfonic acid modified is obtained by mixing the process of mixture and (B-2) will be upper
State the process that mixture carries out melting extrusion granulation.
(B-1) in process, preferably slightly water-soluble pesticide activity is uniformly mixed with solid dielectric.
While said mixture is heated to temperature or the work of slightly water-soluble pesticide of more than the Tg of for example above-mentioned solid dielectric
Property compound fusing point more than temperature, while carry out (B-2) process.
(B-2) process can for example use prilling granulator.As the prilling granulator, for example, Three Tec are public
Take charge of the Mini extruder ZE-9 types of system.
In extrusion by melting, it can also be further equipped be cooled to room temperature the granules obtained in (B-2) process
Process ((B-3) process).In addition, as needed, before and after (B-3) process granules can be carried out with whole grain, broken or powder
It is broken.
Ultrasonic wave pressed disc method is the method for for example possessing following processes：(C-1) by slightly water-soluble pesticide activity and
Saponified solid dielectric comprising sulfonic acid modified polyvinyl acetate be obtained by mixing the process and (C- of mixture
2) mixture obtained in above-mentioned operation is filled to the alms bowl of ultrasonic wave tablet press machine, irradiates ultrasonic wave while being pressed
The process of piece.
(C-1) in process, preferably slightly water-soluble pesticide activity is uniformly mixed with solid dielectric.
As the ultrasonic wave tablet press machine used in (C-2) process, for example, Tecnea Engineering companies
The ultrasonic wave forming machine USTM/L20 of system.In this process, ultrasonic irradiation energy can be 600~2000J, or 700
~1800J, or 800~1300J.
It should be noted that in the manufacture method of composition of the present embodiment, slightly water-soluble pesticide activity chemical combination
The concrete example and suitable morphology of thing and saponified solid dielectric comprising sulfonic acid modified polyvinyl acetate are related to composition
And embodiment it is identical.In addition, the mass ratio of slightly water-soluble pesticide activity and solid dielectric in composition and
Slightly water-soluble pesticide activity can such as pass through with saponified mass ratio in (A-1), (B-1) and (C-1) process
Their mixing ratio etc. is adjusted to be adjusted.
(composition pesticide)
The composition that the above embodiment is related to such as can also by adding formulation auxiliary agents additional component agriculture is made
Drug composition.
The composition pesticide that one embodiment is related to contains the composition that the above embodiment is related to.The composition pesticide
Raising slightly water-soluble pesticide activity water miscible excellent performance.
Above-mentioned composition pesticide can contain at least one formulation auxiliary agents.
As above-mentioned formulation auxiliary agents, for example, surfactant, solid carrier and adhesive.
As above-mentioned surfactant, nonionic surfactant, cationic surfactant and the moon can be enumerated
Ionic surfactant.
As nonionic surfactant, for example, the acrylic copolymer such as acrylic acid graft copolymer, poly-
Ethylene oxide alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene lanolin alcohol, the condensation product of polyoxyethylene alkylphenol and formaldehyde
(polyoxyethylene alkylphenol formaldehyde condensation products), polyoxyethylene sorbitan carboxylic ester, polyoxyethylene glycerol mono fatty acid ester, gather
Propylene glycol mono, Polyoxyethylene Sorbitol Fatty Acid Esters, sorbitan carboxylic esters, Emulsifier EL-60, polyoxy
Ethene fatty acid ester, higher fatty acid ester, sucrose fatty ester, polyoxyethylene polyoxypropylene block polymer, polyoxy second
Alkene fatty acid amide and polyoxyethylene alkyl amine.
As cationic surfactant, for example, the alkylamine hydrochloride such as dodecylamine hydrochloride；Alkyl quaternary
The alkyl trimethyl quaternary ammonium salts such as ammonium salt, dodecyl trimethyl ammonium salt；Alkyl dimethyl benzyl ammonium salt, alkyl salt, alkane
Base isoquinolin salt, dialkylmorpholinum salts, benzethonium chloride and poly- alkylvinylpyridines salt.
As anionic surfactant, for example, the lignosulfonates such as lignin sulfonic acid sodium salt；Naphthalene sulphur
The salt of the condensation product of the aryl sulfonic acids such as the sodium salt (naphthalene sulfonic acid-formaldehyde condensation product sodium salt) of condensation product of acid and formaldehyde and formaldehyde is (following
Sometimes referred to as " salt of aryl sulfonic acid formaldehyde condensation products ")；Sodium salt (the methyl naphthalene sulfonic acid first of the condensation product of methyl naphthalene sulfonic acid and formaldehyde
Aldehyde condensate sodium salt or methyl naphthalene sulfonic acid and formaldehyde condensation polymer sodium salt) etc. the condensation product of alkyl aryl sulphonic acid and formaldehyde salt it is (following
Sometimes referred to as " salt of alkyl aryl sulphonic acid formaldehyde condensation products ")；The sodium salt of naphthalene sulfonic acids and the condensation product of butyl naphthalene sulfonic acids and formaldehyde
The condensation product of aryl sulfonic acids such as (naphthalene sulfonic acids butyl naphthalene sulfonic acid-formaldehyde condensation product sodium salts) and alkyl aryl sulphonic acid and formaldehyde salt (with
Down sometimes referred to as " salt of the formaldehyde condensation products of aryl sulfonic acid and alkyl aryl sulphonic acid ")；The sodium soaps such as sodium palmitate；Polyoxy second
The ether carboxylic acid sodiums such as alkene lauryl alcohol carboxylic acid sodium；The higher fatty acids such as sodium N-lauroyl sarcosinate, N- sodium lauroyl glutamates
The salt of amino condensation compound；Senior alkyl sulfonate；The advanced fatty acid ester sulfonate such as laurate sulfonate；Dioctyl sulfo group
The dialkyl sulfosuccinates such as sodium succinate；The high fatty acid amide sulfonate such as oleamide sulfonate；Detergent alkylate sulphur
The alkylaryl sulfonates such as hydrochlorate, diisopropyl naphthalene sulfonate；Alkenyl sulfonate；Lauryl sodium sulfate salt, pentadecane -2- sulphur
The fatty alcohol sulfate salts such as acid esters salt；The polyoxyethylene alkyl ether sulfuric acid such as sodium laureth sulfate；And
The polyoxyethylene alkyl phosphate salt such as two polyoxyethylene lauryl ether phosphate ester salts.
Above-mentioned surfactant can be used singly or in combination of two or more.
When above-mentioned composition pesticide contains surfactant, total content of surfactant is relative to composition pesticide
Gross mass for example can be more than 0.1 mass %, more than 0.5 mass % or more than 1 mass %, or 50 mass % with
Under, below 30 mass %, below 20 mass % or below 10 mass %.From these viewpoints, the total of surfactant contains
Amount for example can be 0.1~50 mass % relative to the gross mass of composition pesticide, or 0.1~30 mass %, also may be used
Think 0.5~20 mass %, or 1~10 mass %.
As above-mentioned solid carrier, for example, water-solubility carrier and non aqueous carrier.As water-solubility carrier,
For example, ammonium sulfate, ammonium hydrogen carbonate, ammonium nitrate, ammonium chloride, potassium chloride, sodium sulphate, magnesium sulfate, sodium citrate, carbonic acid
Carbohydrate and the urea such as organic acid, sucrose, the lactose such as the organic or inorganic such as sodium, sodium acid carbonate Barbiturates, citric acid, butanedioic acid.
As non aqueous carrier, for example, the clay such as kaolin class, calcium carbonate, montmorillonite, diatomite, zeolite, green slope thread
Stone, gypsum, pottery stone, float stone, wood powder, perlite, volcanic sand (volcanic sand) and hard charcoal.Solid carrier can individually make
With a kind, two or more can also be applied in combination.
When above-mentioned composition pesticide contains solid carrier, total content of solid carrier relative to composition pesticide total matter
Amount for example can be more than 0.1 mass %, more than 0.5 mass % or more than 1 mass %, or below 90 mass %, 60
Below quality % or below 30 mass %.From these viewpoints, total content of solid carrier is relative to composition pesticide
Gross mass for example can be 0.1~90 mass %, or 0.5~60 mass %, or 1~30 mass %.
As above-mentioned adhesive, for example, sodium carboxymethylcellulose, methylcellulose, methylethylcellulose,
Bassora gum, alphalysed starch, dextrin, alginic acid and sodium alginate.Adhesive can be used alone, and can also be applied in combination 2 kinds
More than.
When above-mentioned composition pesticide contains adhesive, total content of adhesive relative to composition pesticide gross mass example
Such as can be more than 0.5 mass %, more than 1 mass % or more than 2 mass %, or below 10 mass %, 5 mass % with
Lower or below 4 mass %.From these viewpoints, total content of adhesive for example may be used relative to the gross mass of composition pesticide
Think 0.5~10 mass %, or 1~5 mass %, or 2~4 mass %.
From the viewpoint of the water solubility for more muchly keeping high slightly water-soluble pesticide activity, composition pesticide
Aromatic sulphonic acid type high molecular surfactant can be contained.That is, composition pesticide of the present embodiment can contain this
The composition and aromatic sulphonic acid type high molecular surfactant that embodiment is related to., can be longer according to the composition pesticide
The water solubility of high slightly water-soluble pesticide activity is kept long.In the composition pesticide, to slightly water-soluble pesticide activity
Compound is not particularly limited, such as can be flumioxazin or 1- [2- ({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls]
Epoxide } methyl) -3- aminomethyl phenyls] -4- methyl -5- oxos -4,5- dihydros -1H-TETRAZOLE.
As aromatic sulphonic acid type high molecular surfactant, for example, lignosulfonates, alkylaryl sulphur
The salt of sour formaldehyde condensation products, the salt of aryl sulfonic acid formaldehyde condensation products and the formaldehyde condensation of aryl sulfonic acid and alkyl aryl sulphonic acid
The salt of thing.From the viewpoint of the water solubility for more muchly keeping high slightly water-soluble pesticide activity, aromatic sulphonic acid
Type high molecular surfactant can be selected from lignosulfonates, the salt of alkyl aryl sulphonic acid formaldehyde condensation products, aryl sulfonic acid
At least one of the salt and aryl sulfonic acid of formaldehyde condensation products and the salt of formaldehyde condensation products of alkyl aryl sulphonic acid.
When composition pesticide contains slightly water-soluble pesticide activity and aromatic sulphonic acid type high molecular surfactant,
From the viewpoint of the water solubility for more muchly keeping high slightly water-soluble pesticide activity, slightly water-soluble pesticide activity
The mass ratio of compound and aromatic sulphonic acid type high molecular surfactant can be 2:1~1:10, or 1:1~1:10,
Can also be 1:5~1:10.That is, in the composition pesticide, (quality of slightly water-soluble pesticide activity)/(aromatic series sulphur
The quality of acid type high molecular surfactant) can be 2/1~1/10, or 1/1~1/10, or 1/5~1/
10。
As the form of composition pesticide, for example, the preparation such as hydrating agents, particle hydrating agents, granula.
(manufacture method of composition pesticide)
Composition pesticide of the present embodiment for example can be by the way that the composition of the above embodiment and surface be lived
Property the formulation auxiliary agents mixing such as agent, solid carrier, adhesive, and the processing such as implement to crush, be granulated, be dry as needed to manufacture.
More specifically, hydrating agents, particle hydrating agents and granula can for example be manufactured by following manufacture method.
(1) hydrating agents
Composition, surfactant and the solid carrier mixing that the above embodiment is related to, and it is dry using aeropulverizer etc.
Formula pulverizer is crushed.
(2) particle hydrating agents
The composition being related to for the above embodiment, as needed and mixed surfactant, adhesive and solid carry
Body, and gained mixture is crushed as needed.Afterwards, add water to be kneaded, carry out extruding pelletization.It is next, right
Gained particle is dried, and is crushed as needed, whole grain and sieving.
(3) granula
The composition being related to for the above embodiment, as needed and mixed surfactant, adhesive and solid carry
Body, and gained mixture is crushed as needed.Afterwards, add water to be kneaded, carry out extruding pelletization.It is next, right
Gained particle is dried, and is crushed as needed, whole grain and sieving.
Embodiment
Hereinafter, embodiment and comparative example are enumerated, more specific description is carried out to the present invention.It is it should be noted that of the invention
It is not limited to following embodiment.
Following make is related to as solid dispersions (powder A~J), the comparative example of composition of the present embodiment
Solid dispersions (comparing powder K, L) and the powder (comparing powder M~S) as physical mixed sample.
Production Example 1 (powder A)
By 10.0 mass parts of flumioxazin and GOHSENX L-823 (saponified, the days of sulfonic acid modified polyvinyl acetate
This synthetic chemical industry Co. Ltd. system) mixing of 90.0 mass parts, it is followed successively by barrel zone temperature from the near-end of powder input port
Under conditions of 50 DEG C, 140 DEG C, 190 DEG C melting extrusion is carried out using Mini-Extruder (Three-Tec company systems, ZE-9 types)
It is granulated.After gained granules are cooled to room temperature, carried out using pulverizer (Nara Machinery Co., Ltd.'s system, DM-6 types)
Crush, obtained the powder A (solid dispersions) as composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder A, the peak as a result unconfirmed for arriving the crystallization from flumioxazin
(Fig. 1).
Production Example 2 (powder B)
The R body mappings of N- (1,1,3- trimethyl indane -4- bases) -1- methyl -3- difluoromethyl pyrazole -4- carboxylic acid amides is different
The 98 of structure body and its S body enantiomters:2 10.0 mass parts of mixture (being denoted as pesticide activity A below) and
GOHSENX L-823 (saponified, the Nippon Synthetic Chemical Industry Co., Ltd's system of sulfonic acid modified polyvinyl acetate) 90.0 matter
Part mixing is measured, is utilized under conditions of barrel zone temperature is followed successively by 50 DEG C, 130 DEG C, 150 DEG C from the near-end of powder input port
Mini-Extruder (Three-Tec company systems, ZE-9 types) carries out melting extrusion granulation.Gained granules are cooled to room temperature
Afterwards, crushed using pulverizer (Nara Machinery Co., Ltd.'s system, DM-6 types), obtained relating to as present embodiment
And composition powder B (solid dispersions).
Carry out the powder x-ray diffraction measure of powder B, the crystallization as a result unconfirmed arrived from pesticide activity A
Peak (Fig. 2).
Production Example 3 (powder C)
By 30.0 mass parts of pesticide activity A and the GOHSENX L-823 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) mixing of 70.0 mass parts, in barrel zone temperature from the near-end of powder input port
Melted under conditions of being followed successively by 50 DEG C, 130 DEG C, 150 DEG C using Mini-Extruder (Three-Tec company systems, ZE-9 types)
Melt extruding pelletization.After gained granules are cooled to room temperature, pulverizer (Nara Machinery Co., Ltd.'s system, DM-6 are utilized
Type) crushed, obtain the powder C (solid dispersions) as composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder C, the crystallization as a result unconfirmed arrived from pesticide activity A
Peak (Fig. 3).
Production Example 4 (powder D)
By 10.0 mass parts of pesticide activity A and the GOHSENX L-3266 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) mixing of 90.0 mass parts, in barrel zone temperature from the near-end of powder input port
Melted under conditions of being followed successively by 90 DEG C, 150 DEG C, 200 DEG C using Mini-Extruder (Three-Tec company systems, ZE-9 types)
Melt extruding pelletization.After gained granules are cooled to room temperature, utilize pulverizer (Nara Machinery Co., Ltd.'s system, SAMF)
Crushed, obtained the powder D (solid dispersions) as composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder D, the crystallization as a result unconfirmed arrived from pesticide activity A
Peak (Fig. 4).
Production Example 5 (powder E)
By 10.0 mass parts of pesticide activity A and ASP-05 (sulfonic acid modified polyvinyl acetate it is saponified,
JAPAN VAM＆POVAL Co. Ltd. systems) mixing of 90.0 mass parts, it is followed successively by barrel zone temperature from the near-end of powder input port
Melting is carried out under conditions of 100 DEG C, 150 DEG C, 180 DEG C using Mini-Extruder (Three-Tec company systems, ZE-9 types) to squeeze
Go out to be granulated.After gained granules are cooled to room temperature, carried out using pulverizer (Nara Machinery Co., Ltd.'s system, SAMF)
Crush, obtained the powder E (solid dispersions) as composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder E, the crystallization as a result unconfirmed arrived from pesticide activity A
Peak (Fig. 5).
Production Example 6 (powder F)
By 20.0 mass parts of Guardian and GOHSENX L-823 (sulfonic acid modified polyvinyl acetate it is saponified, Japanese
Synthetic chemical industry Co. Ltd. system) 80.0 mass parts are dissolved in acetone/ethanol (35/65, mass ratio) mixed liquid medium 900
Mass parts, using spray dryer (spray dryer B-290, buchi company system) 70~85 DEG C of inlet temperature, flow 6~
It is spray-dried under conditions of 9mL/ minutes, has obtained the powder F (solid dispersions) as composition of the present embodiment.
The powder x-ray diffraction measure of powder F is carried out, as a result confirms the peak of some crystallizations from Guardian,
But compared to powder Q (Figure 17) is compared, peak intensity reduces (Fig. 6).
Production Example 7 (powder G)
By 2- [3- (ethylsulfonyl) pyridine -2- bases], (trifyl) benzoxazoles (are denoted as pesticide activity to -5- below
Compound B) 10.0 mass parts and GOHSENX L-823 (the chemical work of saponified, Japanese synthesis of sulfonic acid modified polyvinyl acetate
Industry Co. Ltd. system) 90.0 mass parts mixing, barrel zone temperature be followed successively by from the near-end of powder input port 50 DEG C, 130 DEG C,
Under conditions of 150 DEG C melting extrusion granulation is carried out using Mini-Extruder (Three-Tec company systems, ZE-9 types).By gained
After granules are cooled to room temperature, are crushed, made using pulverizer (Nara Machinery Co., Ltd.'s system, SAMF)
For the powder G (solid dispersions) of composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder G, the crystallization as a result unconfirmed arrived from pesticide activity B
Peak (Fig. 7).
Production Example 8 (powder H)
By 10.0 mass parts of pesticide activity B and the GOHSENX L-3266 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) mixing of 90.0 mass parts, in barrel zone temperature from the near-end of powder input port
Melted under conditions of being followed successively by 90 DEG C, 130 DEG C, 200 DEG C using Mini-Extruder (Three-Tec company systems, ZE-9 types)
Melt extruding pelletization.After gained granules are cooled to room temperature, utilize pulverizer (Nara Machinery Co., Ltd.'s system, SAMF)
Crushed, obtained the powder H (solid dispersions) as composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder H, the crystallization as a result unconfirmed arrived from pesticide activity B
Peak (Fig. 8).
Production Example 9 (powder I)
By 10.0 mass parts of pesticide activity B and ASP-05 (sulfonic acid modified polyvinyl acetate it is saponified,
JAPAN VAM＆POVAL Co. Ltd. systems) mixing of 90.0 mass parts, it is followed successively by barrel zone temperature from the near-end of powder input port
Under conditions of 90 DEG C, 150 DEG C, 200 DEG C melting extrusion is carried out using Mini-Extruder (Three-Tec company systems, ZE-9 types)
It is granulated.After gained granules are cooled to room temperature, powder is carried out using pulverizer (Nara Machinery Co., Ltd.'s system, SAMF)
It is broken, obtain the powder I (solid dispersions) as composition of the present embodiment.
Carry out the powder x-ray diffraction measure of powder I, the crystallization as a result unconfirmed arrived from pesticide activity B
Peak (Fig. 9).
Production Example 10 (powder J)
By 1- [2- ({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls] epoxide } methyl) -3- aminomethyl phenyls] -4- methyl -5-
Oxo -4,5- dihydros -10.0 mass parts of 1H-TETRAZOLE (being denoted as pesticide activity C below) and GOHSENX L-823 (sulfonic acid
Saponified, the Nippon Synthetic Chemical Industry Co., Ltd's system of modified polyvinyl acetate) mixing of 90.0 mass parts, in barrel zone temperature
Mini-Extruder (Three-Tec are utilized under conditions of 50 DEG C, 130 DEG C, 150 DEG C are followed successively by from the near-end of powder input port
Company system, ZE-9 types) carry out melting extrusion granulation.After gained granules are cooled to room temperature, using pulverizer, (how is Co., Ltd.
Good machinery production is made, SAMF) crushed, (solid disperses the powder J for having obtained as composition of the present embodiment
Body).
Carry out the powder x-ray diffraction measure of powder J, the crystallization as a result unconfirmed arrived from pesticide activity C
Peak (Figure 10).
Production Example 11 (compares powder K)
By 10.0 mass parts of flumioxazin and GOHSENOL GL-05S (saponified, the Japanese synthesis of polyvinyl acetate
Chemical industry Co. Ltd. system) 90.0 mass parts mixing, barrel zone temperature be followed successively by from the near-end of powder input port 50 DEG C,
Under conditions of 140 DEG C, 190 DEG C melting extrusion granulation is carried out using Mini-Extruder (Three-Tec company systems, ZE-9 types).
After gained granules are cooled to room temperature, crushed using pulverizer (Nara Machinery Co., Ltd.'s system, DM-6 types)
And obtain comparing powder K.
The powder x-ray diffraction measure of powder K is carried out, as a result confirms the peak of some crystallizations from flumioxazin
(Figure 11).
Production Example 12
By 10.0 mass parts of flumioxazin and POVACOAT (polyvinyl alcohol acrylic arid methacrylic acid copolymer,
Daido Chemical Corp's system) mixing of 90.0 mass parts, in barrel zone temperature 50 are followed successively by from the near-end of powder input port
DEG C, 140 DEG C, carry out melting extrusion using Mini-Extruder (Three-Tec company systems, ZE-9 types) under conditions of 190 DEG C and make
Grain, but can not extrude.
Production Example 13 (compares powder L)
By 10.0 mass parts of pesticide activity A and GOHSENOL GL-05S (saponified, the days of polyvinyl acetate
This synthetic chemical industry Co. Ltd. system) mixing of 90.0 mass parts, it is followed successively by barrel zone temperature from the near-end of powder input port
Under conditions of 50 DEG C, 130 DEG C, 150 DEG C melting extrusion is carried out using Mini-Extruder (Three-Tec company systems, ZE-9 types)
It is granulated.After gained granules are cooled to room temperature, carried out using pulverizer (Nara Machinery Co., Ltd.'s system, DM-6 types)
Crush and obtain comparing powder L.
The powder x-ray diffraction measure of powder L is carried out, as a result confirms crystallization from pesticide activity A
Peak (Figure 12).
Production Example 14 (compares powder M (physical mixed sample))
By 10.0 mass parts of pesticide activity A and the GOHSENX L-3266 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) 90.0 mass parts are fitted into bag and are vibrated and mixed, so as to be compared
Compared with powder M (physical mixed sample).
The powder x-ray diffraction measure of powder M is carried out, as a result confirms crystallization from pesticide activity A
Peak (Figure 13).
Production Example 15 (compares powder N (physical mixed sample))
By 10.0 mass parts of pesticide activity A and ASP-05 (sulfonic acid modified polyvinyl acetate it is saponified,
JAPAN VAM＆POVAL Co. Ltd. systems) 90.0 mass parts are fitted into bag and are vibrated and mixed, so as to obtain comparing powder
N (physical mixed sample).
The powder x-ray diffraction measure of powder N is carried out, as a result confirms crystallization from pesticide activity A
Peak (Figure 14).
Production Example 16 (compares powder O (physical mixed sample))
By 20.0 mass parts of Guardian and GOHSENX L-823 (sulfonic acid modified polyvinyl acetate it is saponified, Japanese
Synthetic chemical industry Co. Ltd. system) 80.0 mass parts are fitted into bag and are vibrated and mixed, so as to obtain comparing powder O
(physical mixed sample).
The powder x-ray diffraction measure of powder O is carried out, as a result confirms the peak (figure of the crystallization from Guardian
15)。
Production Example 17 (compares powder P (physical mixed sample))
By 10.0 mass parts of pesticide activity B and the GOHSENX L-823 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) 90.0 mass parts are fitted into bag and are vibrated and mixed, so as to be compared
Compared with powder P (physical mixed sample).
The powder x-ray diffraction measure of powder P is carried out, as a result confirms crystallization from pesticide activity B
Peak (Figure 16).
Production Example 18 (compares powder Q (physical mixed sample))
By 10.0 mass parts of pesticide activity B and the GOHSENX L-3266 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) 90.0 mass parts are fitted into bag and are vibrated and mixed, so as to be compared
Compared with powder Q (physical mixed sample).
The powder x-ray diffraction measure of powder Q is carried out, as a result confirms crystallization from pesticide activity B
Peak (Figure 17).
Production Example 19 (compares powder R (physical mixed sample))
By 10.0 mass parts of pesticide activity B and ASP-05 (sulfonic acid modified polyvinyl acetate it is saponified,
JAPAN VAM＆POVAL Co. Ltd. systems) 90.0 mass parts are fitted into bag and are vibrated and mixed, so as to obtain comparing powder
R (physical mixed sample).
The powder x-ray diffraction measure of powder R is carried out, as a result confirms crystallization from pesticide activity B
Peak (Figure 18).
Production Example 20 (compares powder S (physical mixed sample))
By 10.0 mass parts of pesticide activity C and the GOHSENX L-823 (soaps of sulfonic acid modified polyvinyl acetate
Compound, the Nippon Synthetic Chemical Industry Co., Ltd's system) 90.0 mass parts are fitted into bag and are vibrated and mixed, so as to be compared
Compared with powder S (physical mixed sample).
The powder x-ray diffraction measure of powder S is carried out, as a result confirms crystallization from pesticide activity C
Peak (Figure 19).
As the composition pesticide of present embodiment, make (be used as this reality comprising above-mentioned powder A, B, C, F and J as follows
The solid dispersions for the composition that the mode of applying is related to) hydrating agents (hydrating agents 1~10).
Production Example 21 (hydrating agents 1)
For 50.0 mass parts of powder A, New Kargen RX-B (Zhu Ben's Oil Corporation's system, sulfomethylated lignin are mixed
Acid sodium-salt) 50.0 mass parts, obtain hydrating agents 1 of the flumioxazin comprising 5.0 mass % as active ingredient.
Production Example 22 (hydrating agents 2)
For 50.0 mass parts of powder A, mixing SUPRAGIL MNS/90 (methyl naphthalene sulfonic acid and formaldehyde condensation polymer sodium salt, Soviet Union
Prestige solar corona Co. Ltd. system) 50.0 mass parts, hydration of the flumioxazin for having obtained containing 5.0 mass % as active ingredient
Agent 2.
Production Example 23 (hydrating agents 3)
For 50.0 mass parts of powder A, New Kargen RX-B (Zhu Ben's Oil Corporation's system, sulfomethylated lignin are mixed
Acid sodium-salt) 25.0 mass parts, obtain hydrating agents 3 of the flumioxazin as active ingredient for containing 6.7 mass %.
Production Example 24 (hydrating agents 4)
For 50.0 mass parts of powder B, mixing Sorpol 5029-0 (lauryl sodium sulfate salt, eastern nation chemical industry
Co. Ltd. system) 3.0 mass parts, DEMOL SN-B (naphthalene sulfonic acids butyl naphthalene sulfonic acid-formaldehyde condensation product sodium salt, Kao Corp
System) 2.0 mass parts, Tokusil GU-N (hard charcoal, Oriental Silicas Corporation systems) 5.0 mass parts and ASP-
400P (kaolin, BASF AG's system) 40.0 mass parts, the pesticide activity A for having obtained containing 5.0 mass %, which is used as, to be had
Imitate the hydrating agents 4 of component.
Production Example 25 (hydrating agents 5)
For 16.7 mass parts of powder C, mixing Sorpol 5029-0 (lauryl sodium sulfate salt, eastern nation chemical industry
Co. Ltd. system) 3.0 mass parts, DEMOL SN-B (naphthalene sulfonic acids butyl naphthalene sulfonic acid-formaldehyde condensation product sodium salt, Kao Corp
System) 2.0 mass parts, Tokusil GU-N (hard charcoal, Oriental Silicas Corporation systems) 5.0 mass parts and ASP-
400P (kaolin, BASF AG's system) 73.3 mass parts, the pesticide activity A for having obtained containing 5.0 mass %, which is used as, to be had
Imitate the hydrating agents 5 of component.
Production Example 26 (hydrating agents 6)
For 25.0 mass parts of powder F, mixing Sorpol 5029-0 (lauryl sodium sulfate salt, eastern nation chemical industry
Co. Ltd. system) 3.0 mass parts, DEMOL SN-B (naphthalene sulfonic acids butyl naphthalene sulfonic acid-formaldehyde condensation product sodium salt, Kao Corp
System) 2.0 mass parts, Tokusil GU-N (hard charcoal, Oriental Silicas Corporation systems) 5.0 mass parts and ASP-
400P (kaolin, BASF AG's system) 65.0 mass parts, have obtained containing the Guardian that active constituent content is 5.0 mass %
Hydrating agents 6.
Production Example 27 (hydrating agents 7)
For 50.0 mass parts of powder J, New Kargen RX-B (Zhu Ben's Oil Corporation's system, sulfomethylated lignin are mixed
Acid sodium-salt) 50.0 mass parts, obtain hydrating agents 7 of the pesticide activity C as active ingredient for containing 5.0 mass %.
Production Example 28 (hydrating agents 8)
For 50.0 mass parts of powder J, New Kargen RX-B (Zhu Ben's Oil Corporation's system, sulfomethylated lignin are mixed
Acid sodium-salt) 25.0 mass parts, obtain hydrating agents 8 of the pesticide activity C as active ingredient for containing 6.7 mass %.
Production Example 29 (hydrating agents 9)
For 50.0 mass parts of powder J, mixing SUPRAGIL MNS/90 (methyl naphthalene sulfonic acid and formaldehyde condensation polymer sodium salt, Soviet Union
Prestige solar corona Co. Ltd. system) 50.0 mass parts, the pesticide activity C for having obtained containing 5.0 mass % is as active ingredient
Hydrating agents 9.
Production Example 30 (hydrating agents 10)
For 50.0 mass parts of powder J, mixing SUPRAGIL MNS/90 (methyl naphthalene sulfonic acid and formaldehyde condensation polymer sodium salt, Soviet Union
Prestige solar corona Co. Ltd. system) 25.0 mass parts, the pesticide activity C for having obtained containing 6.7 mass % is as active ingredient
Hydrating agents 10.
(evaluation)
For powder A~J (solid dispersions), compare powder K~L (solid dispersions), comparing powder M~S, (physics mixes
Close sample) and hydrating agents 1~10, water solubility is determined by the following method.It should be noted that measuring temperature is set to
25℃。
[the water solubility measure of flumioxazin]
In the case of solid dispersions, by 2.5g (being calculated as 250mg with flumioxazin) inputs to 3 degree of hard water 900mL
In, in the case of hydrating agents, by 5.0g (being calculated as 250mg with flumioxazin) inputs into 3 degree of hard water 900mL, carry out acute
Strong stirring.After stirring has started 15 minutes, 1 it is small when after, 6 it is small when after at the time of, extract mixed liquor a part as experiment
Liquid.It should be noted that persistently stir in test.Experimental liquid is filtered with 0.45 μm of filter.Utilize efficient liquid phase
The concentration of flumioxazin of the chromatography to containing in filtrate is analyzed, and the water that gained concentration is set to flumioxazin dissolves
Degree.Individually the water solubility at 25 DEG C is 2ppm to flumioxazin, as benchmark water solubility increase rate (times
Rate).
[the water solubility measure of pesticide activity A]
In the case of solid dispersions, 1.0~3.0g (being calculated as 300mg with pesticide activity A) is put into 3 degree
In hard water 500mL, in the case of hydrating agents, by 2.5g (being calculated as 125mg with pesticide activity A) inputs to 3 degree of hard water
In 500mL, it is vigorously stirred.It should be noted that persistently stirred in experiment.After stirring has started 30 minutes, 1 it is small when
Afterwards, 5 it is small when after at the time of, extract a part for mixed liquor as experimental liquid.Experimental liquid is filtered with 0.45 μm of filter.
Analyzed using the concentration of pesticide activity A of the high performance liquid chromatography to being included in filtrate, using gained concentration as agriculture
The water solubility of medicine reactive compound A.Individually the water solubility at 25 DEG C is 20ppm to pesticide activity A, as base
Standard calculates the increase rate (multiplying power) of water solubility.
[the water solubility measure of Guardian]
In the case of solid dispersions and physical mixed sample, by 625mg (being calculated as 125mg with Guardian) inputs extremely
In 3 degree of hard water 500mL, in the case of hydrating agents, by 2.5g (being calculated as 125mg with Guardian) inputs to 3 degree of hard water 500mL
In, it is vigorously stirred.It should be noted that persistently stirred in experiment.After stirring has started 15 minutes, 1 it is small when after, it is 6 small
When after at the time of, extract a part for mixed liquor as experimental liquid.Experimental liquid is filtered with 0.45 μm of filter.Utilize height
The concentration of Guardian of the effect liquid phase chromatogram to being included in filtrate is analyzed, and is dissolved gained concentration as the water of Guardian
Degree.Individually the water solubility at 25 DEG C is 5ppm to Guardian, as the increase rate (multiplying power) of benchmark water solubility.
[the water solubility measure of pesticide activity B]
In the case of solid dispersions, by 5.4g (being calculated as 540mg with pesticide activity B) inputs to 3 degree of hard water
In 900mL, it is vigorously stirred.It should be noted that persistently stirred in experiment.After stirring has started 15 minutes, 1 it is small when
Afterwards, 5 it is small when after at the time of, extract a part for mixed liquor as experimental liquid.Experimental liquid is filtered with 0.45 μm of filter.
Analyzed by the concentration of pesticide activity B of the high performance liquid chromatography to being included in filtrate, using gained concentration as agriculture
The water solubility of medicine reactive compound B.Individually the water solubility at 25 DEG C is 6ppm to pesticide activity B, as base
Standard calculates the increase rate (multiplying power) of water solubility.
[the water solubility measure of pesticide activity C]
In the case of solid dispersions, by 300mg (being calculated as 30mg with pesticide activity C) inputs to 3 degree of hard water
In 900mL, in the case of hydrating agents, by 447~600mg (being calculated as 30mg with pesticide activity C) inputs to 3 degree of hard water
In 900mL, it is vigorously stirred.It should be noted that persistently stirred in experiment.After stirring has started 15 minutes, 1 it is small when
Afterwards, 5 it is small when after at the time of, extract a part for mixed liquor as experimental liquid.Experimental liquid is filtered with 0.45 μm of filter.
Analyzed using the concentration of pesticide activity C of the high performance liquid chromatography to being included in filtrate, using gained concentration as agriculture
The water solubility of medicine reactive compound C.Individually the water solubility at 25 DEG C is 0.03ppm to pesticide activity C, as
The increase rate (multiplying power) of benchmark water solubility.
By water solubility measure the results are shown in table 1, table 2, table 3 and table 4.By the increase rate of water solubility the results are shown in
Table 5, table 6, table 7 and table 8." N.D. " in table refers to below detection limit.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
[table 7]
[table 8]
According to the result of table 5 and table 6：Powder (comparing powder K~S) is compared compared with, of the present embodiment
Raising of the composition (powder A~J, Production Example 1~10) in the water solubility of the slightly water-soluble pesticide activity at each moment
Rate (improving water miscible performance) is excellent.
In addition, according to the result of table 1 and table 3：Compared with the powder A (Production Example 1) as solid dispersions, manufacture
The hydrating agents 1~3 of example 21~23 (are lived containing N- phenylphthalimides compound and aromatic sulphonic acid type macromolecule surface
The composition pesticide of property agent) high water solubility after 6 hours, it can more muchly keep N- phenylphthalimides
The highly-water-soluble of compound.
In addition, according to the result of table 1 and table 4：Compared with the powder J (Production Example 10) as solid dispersions, system
Make (the agriculture containing pesticide activity C and aromatic sulphonic acid type high molecular surfactant of hydrating agents 7~10 of example 27~30
Drug composition) high water solubility after 5h, it can more muchly keep the highly-water-soluble of pesticide activity C.
Claims (12)
1. a kind of composition, it includes slightly water-soluble pesticide activity and solid dielectric, the solid dielectric contains
Saponified, the slightly water-soluble pesticide work of polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group
Property compound is scattered in the solid dielectric.
2. composition according to claim 1, wherein, the slightly water-soluble pesticide activity with it is described saponified
Mass ratio is 7:3~1:15.
3. composition according to claim 1 or 2, wherein, the saponified saponification degree is 10~100mol%.
4. according to composition according to any one of claims 1 to 3, wherein, the slightly water-soluble pesticide activity is
Flumioxazin, N- (1,1,3- trimethyl indane -4- bases) -1- methyl -3- difluoromethyl pyrazole -4- carboxylic acid amides, 1- [2-
({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls] epoxide } methyl) -3- aminomethyl phenyls] -4- methyl -5- oxo -4,5- dihydros -
1H-TETRAZOLE, Guardian or 2- [3- (ethylsulfonyl) pyridine -2- bases] -5- (trifyl) benzoxazoles.
5. a kind of manufacture method of composition, it possesses：
The process that slightly water-soluble pesticide activity and solid dielectric are dissolved in organic solvent and prepare solution,
The solid dielectric is included containing the polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group
It is saponified；With
The process that the solution is spray-dried.
6. a kind of manufacture method of composition, it possesses：
Slightly water-soluble pesticide activity and solid dielectric are obtained by mixing to the process of mixture,
The solid dielectric is included containing the polyvinyl acetate selected from least one of sulfonic group and sulphonate-base group
It is saponified；With
The process that the mixture is carried out to melting extrusion granulation.
7. a kind of composition, it is manufactured by the manufacture method described in claim 5 or claim 6.
8. a kind of composition pesticide, it contains the composition any one of Claims 1 to 4 and 7.
9. a kind of composition pesticide, it contains the composition and aromatic sulphonic acid any one of Claims 1 to 4 and 7
Type high molecular surfactant.
10. composition pesticide according to claim 9, wherein, the aromatic sulphonic acid type high molecular surfactant is
The salt of the condensation product of the salt of condensation product selected from lignosulfonates, alkyl aryl sulphonic acid and formaldehyde, aryl sulfonic acid and formaldehyde, with
And at least one of aryl sulfonic acid and salt of condensation product of alkyl aryl sulphonic acid and formaldehyde.
11. the composition pesticide according to claim 9 or 10, wherein, the slightly water-soluble pesticide activity and institute
The mass ratio for stating aromatic sulphonic acid type high molecular surfactant is 2:1~1:10.
12. the composition pesticide according to any one of claim 9~11, wherein, the slightly water-soluble pesticide activity
Compound for flumioxazin or 1- [2- ({ [1- (4- chlorphenyls) -1H- pyrazole-3-yls] epoxide } methyl) -3- aminomethyl phenyls] -
4- methyl -5- oxos -4,5- dihydros -1H-TETRAZOLE.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-174433 | 2015-09-04 | ||
| JP2015174433 | 2015-09-04 | ||
| PCT/JP2016/075703 WO2017038946A1 (en) | 2015-09-04 | 2016-09-01 | Composition, method for producing composition, and pesticide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107920528A true CN107920528A (en) | 2018-04-17 |
Family
ID=58188589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680049766.6A Pending CN107920528A (en) | 2015-09-04 | 2016-09-01 | Composition, the manufacture method of composition and composition pesticide |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20180213771A1 (en) |
| EP (1) | EP3345482B1 (en) |
| JP (1) | JP6764412B2 (en) |
| CN (1) | CN107920528A (en) |
| AR (1) | AR105887A1 (en) |
| AU (1) | AU2016317605B2 (en) |
| BR (1) | BR112017027730B1 (en) |
| CA (1) | CA2996680C (en) |
| WO (1) | WO2017038946A1 (en) |
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| CN103897089A (en) * | 2014-04-01 | 2014-07-02 | 湖南省湘维有限公司 | Crystalloid modified polyvinyl alcohol with low viscosity and preparation method thereof |
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-
2016
- 2016-09-01 WO PCT/JP2016/075703 patent/WO2017038946A1/en active Application Filing
- 2016-09-01 BR BR112017027730-1A patent/BR112017027730B1/en active IP Right Grant
- 2016-09-01 AU AU2016317605A patent/AU2016317605B2/en active Active
- 2016-09-01 CN CN201680049766.6A patent/CN107920528A/en active Pending
- 2016-09-01 EP EP16841975.2A patent/EP3345482B1/en active Active
- 2016-09-01 AR ARP160102669A patent/AR105887A1/en active IP Right Grant
- 2016-09-01 JP JP2017538112A patent/JP6764412B2/en active Active
- 2016-09-01 US US15/742,088 patent/US20180213771A1/en not_active Abandoned
- 2016-09-01 CA CA2996680A patent/CA2996680C/en active Active
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|---|---|---|---|---|
| US3791811A (en) * | 1970-01-14 | 1974-02-12 | Hoechst Ag | Storable highly concentrated pesticides and process for their manufacture |
| JPS58131902A (en) * | 1982-02-01 | 1983-08-06 | Toagosei Chem Ind Co Ltd | Liquid agricultural chemical |
| JPH035404A (en) * | 1989-06-01 | 1991-01-11 | Sanyo Chem Ind Ltd | Dispersant for killing hydrating agent |
| CN1192677A (en) * | 1995-08-11 | 1998-09-09 | 日产化学工业株式会社 | Method for making hardly soluble medicine amorphous |
| EP0794198A1 (en) * | 1996-03-06 | 1997-09-10 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Modified polyvinyl alcohol |
| JPH101403A (en) * | 1996-06-12 | 1998-01-06 | Dai Ichi Kogyo Seiyaku Co Ltd | Agrochemical granular agent composition |
| JP2002293702A (en) * | 2001-01-23 | 2002-10-09 | Hokko Chem Ind Co Ltd | Aqueous suspension formulation for directly spraying on paddy field under flooding |
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Also Published As
| Publication number | Publication date |
|---|---|
| BR112017027730B1 (en) | 2022-05-10 |
| BR112017027730A2 (en) | 2018-09-11 |
| CA2996680C (en) | 2023-05-16 |
| JP6764412B2 (en) | 2020-09-30 |
| EP3345482B1 (en) | 2021-11-17 |
| AU2016317605B2 (en) | 2021-01-07 |
| EP3345482A4 (en) | 2019-03-06 |
| AU2016317605A1 (en) | 2018-02-01 |
| AR105887A1 (en) | 2017-11-22 |
| US20180213771A1 (en) | 2018-08-02 |
| EP3345482A1 (en) | 2018-07-11 |
| CA2996680A1 (en) | 2017-03-09 |
| WO2017038946A1 (en) | 2017-03-09 |
| JPWO2017038946A1 (en) | 2018-06-21 |
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